Polymerization and recovery of olefin polymers



April l, 1969 .1.w. DAvlsoN 3,435,380

POLYMERIZATION AND RECOVERY OF OLEFIN POLYMERS Filed Nov. l2, 1964 L qiq BY%7 A 7' TORNEVS United States Patent Office 3,435,380 Patented Apr. l, 1969 3,436,380 POLYMERIZATION AND RECGVERY F OLEFIN POLYMERS Joseph W. Davison, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware Filed Nov. 12, 1964, Ser. No. 410,426 Int. Cl. C081 1/42, 1/88, 1/06 U.S. Cl. Mtl-80.78 8 Claims ABSTRACT 0F THE DISCLOSURE This invention relates to the polymerization and recovery of olefin polymers. ln one aspect, it relates to a slurry type polymerization process for production of olefin polymers. ln another aspect, it relates to a process of copolymerizing ethylene and propylene, with or without a third monomer. t

It is known that copolymers of l-monoolefins, such as ethylene and propylene, can be prepared with an organometallic type catalyst, frequently referred to as a coordination catalyst. Currently, of considerable interest, are amorphous polymers of olefins such as ethylene and propylene having elastomeric properties. It is also known that monomers, such as ethylene and propylene, can be polymerized under conditions such that the polymer product is obtained as a slurry in the hydrocarbon diluent employed as the reaction medium.

The following are objects of this invention.

An object of this invention is to provide an improved process for the polymerization and recovery of olen polymers. A further object of the invention is to provide a slurry process in `which ethylene and propylene, with or without a third monomer, are polymerized in a slurry process in which an improved process of polymer recovery and purification is used. A further object of this invention is to provide such a slurry polymerization process wherein improved temperature and pressure control of the reaction zone is obtained.

Other objects and advantages of this invention will be apparent to one skilled in the art upon reading this disclosure which includes A drawing showing, in schematic form, apparatus suitable for carrying out the process of my invention.

The present invention is concerned with a process for polymerizing a mixture of monoolefns under conditions such that the polymer products are obtained as a slurry in the reaction medium. The invention is also concerned with an improved washing process including the step of using one of the materials supplied to the reaction zone as the washing medium. Also, the invention provides a novel method of controlling pressure and temperature conditions in the reaction zone.

Thus, the invention resides in a process comprising polymerizing a mixture of at least two l-monoolefins with a polymerization coordination catalyst in the presence of a low molecular weight saturated hydrocarbon and under conditions such that a slurry of solid polymer in hydrocarbon diluent is formed in a reaction zone, the steps comprising, introducing one of the oletins to said reaction zone, passing slurry from said reaction zone to a wash zone, countercurently washing slurry in said wash zone with a second olefin being polymerized to remove catalyst and unreacted olefins therefrom, passing the resulting stream of catalyst and unreacted olefins to said reaction zone, passing washed polymer slurry to a steam stripping zone wherein low molecular weight hydrocarbons are stripped from said polymer producing a water slurry of said polymer, removing an overhead vapor stream from the upper portion of said reaction zone, cooling said overhead stream to condense the same, pasing the condensed overhead stream to an accumulation zone, controlling feed of said low molecular weight saturated hydrocarbon fed to said reaction zone in response to changes of liquid level in said accuculation zone to maintain a constant amount of low molecular weight hydrocarbon in the system to maintain the desired boiling point in the reaction zone, recycling liquid from said accumulation zone to said reaction zone, and controlling flow of said recycle stream to maintain a constant liquid level in said reaction zone.

The invention can probably best be understood by first considering the drawing which is provided to illustrate the process. The important pieces of apparatus used in the process of the invention include a reaction zone 11, an accumulation zone 12, a washing zone 13, a steam stripping zone 14, a knockout zone 16, and a dryer 17. Both reaction zone 11 and steam stripping zone 14 are provided with agitation means. The primary feed conduits to the system include ethylene supply conduit 18, ethane supply conduit 19, and propylene supply conduit 21. Ethylene supply conduit preferably extends directly to the reactor. Valved conduits 22 and 23, communicating with conduit 19, are provided so that ethane or other low molecular weight nonreactive hydrocarbon can be supplied to reaction zone 11 or to wash zone 1'3. Valved conduits 24 and 26 are communicate with propylene supply conduit 21 and permit supplying propylene directly to reaction zone 11 or to lwash zone 13. Reaction zone 11 is also supplied with additional inlet conduits. One of these, designated as conduit 27, is provided to supply catalyst to the reaction zone. While I have shown one conduit 27, it is sometimes desirable to supply the separate ingredients of a multicomponent catalyst in separate streams. In other cases, it is desirable to mix these ingredients prior to introduction into the reaction zone. Conduit 28 is provided to supply a termonomer to the reaction zone, the function of the termonomer being more fully explained hereinafter. Conduit 29 is provided to supply a modifier to reaction zone 11, the function of and examples of suitable modifiers also being more fully described hereinafter. Conduit 3'1, provided with pump 32, communicates with reaction zone 11 and `wash zone 13y and is provided to transfer slurry from reaction zone 11 to wash zone 13. Conduit 31 communicates with an intermediate portion of wash zone 13. Also extending between and communicating with reaction zone 11 and wash zone 131 is conduit 331 which serves to transfer liquid from wash zone 13 to reaction zone 11.

Conduit 34, having condenser 316 therein, communicates `with the vapor space of reaction zone 11 and the inlet to accumulation zone 12. Conduit 37 extends from the liquid removal outlet of accumulation zone 12 to the lower end portion of reaction zone 11.

Two liquid level controls are provided in the system including reaction zone 11. These include level controller 38 operatively connected to accumulation zone 12 and valve 39 in conduit 19 by means of line 41. Level controller 42 measures the liquid level in reaction zone 11 and is operatively connected to valve 43 by means of line 44.

Extending from the lower end portion of wash zone 13 is conduit 46 which extends to Ian intermediate portion of stripping zone 14. Steam and water are supplied to stripping zone 14 by means of conduits 47 and 48, respectively. The product is removed from the lower end portion of stripping zone 14 through conduit 49. Extending from the vapor section of stripping zone 14 is conduit 51, this conduit having condenser ,52 therein and extending to knockout zone 16. Water removal conduit 53 and hydrocarbon removal conduit 54 extend from knockout zone 16. Conduit 54 communicates with dryer 17 and the outlet from dryer 17, conduit 56, extends to the inlet of wash zone 13.

In the operation of this system, the monomers are polymerized under conditions to provide a slurry of polymer in reaction zone 11. In the specific modification shown in the drawing, one of ethane or propylene is fed with the ethylene directly to the reaction zone. The other of these materials is used as the wash liquid. The slurry from the reaction zone is passed to wash zone 13 wherein it is washed countercurrently with the wash liquid supplied to the lower end portion of the zone. The wash zone liquid effluent, containing unreacted monomer, the nonreactive hydrocarbon, and catalyst is returned to the reaction zone 11 through conduit 33. Thus, all of the nonreactive hydrocarbon, the ethane in this example, or the propylene, is used as the wash liquid in the system. A slurry of the polymer in the mixed hydrocarbon stream is then passed to the steam stripping zone wherein the remaining catalyst and low molecular weight hydrocarbons are stripped from the polymer producing an aqueous slurry thereof. This material, removed by conduit 49, is then ready for further processing steps.

The vapor mixture obtained from the upper end portion of stripping zone 14 then passes to knockout zone 16 wherein separate water (53) and hydrocarbon (54) streams are obtained. The hydrocarbon stream, after drying, is returned to the wash zone. The water can be discarded or all or a part thereof returned to steam stripping zone 14.

One feature of my invention includes the reaction zone 12 control which is based upon the use of ethane to control the physical conditions (temperature and pressure) so that the desired boiling point or bubble point is maintained therein. Such condition should be maintained constant so that a polymer product of consistent properties is produced. Level controller 38 measures the level in accumulation zone 12 and serves to control total ethane content in the system. This provides for supplying makeup ethane for that used in the process. Level controller 42 maintains a constant level in the reaction zone by controlling recycle of liquid materials from accumulation zone 12 to reaction zone 11. By control of this recycle stream, a constant liquid level is maintained in the reaction zone.

The present invention is particularly applicable to the copolymerization of ethylene and propylene. However, other mixtures of l-monoolefins can also be polymerized, particularly mixtures of ethylene and l-monoolefins represented `by the general formula CHzzCHR, where R is an alkyl radical containing from 1 to 6 carbon atoms. In addition to propylene, examples of suitable 1- monoolefins represented by this formula include 1-butene, l-pentene, l-hexene, l-octene, 3-methyl-1-butene, 3- methyl-l-pentene, 3-methyl-1-hexene, 4-ethyl-1-hexene, 4,4-dimethyl-1-pentene, 3,3-dimethyl-1-butene, S-methyll-hexene, 5methyl1-heptene, 4-methyl-1-heptene, 4,4- dimethyl-l-hexene, -methyl-l-heptene, 3,4,4-trimethyll-pentene, and the like.

The present invention is also applicable to the preparation of terpolymers of l-monoolefins, such as ethylene and propylene, and a third monomer. The third monomer introduces unsaturation into the polymer chain and renders the product sulfur vulcanizable. Examples of suitable termonomers include dicyclopentadiene; ethynyl ethylenes, such as vinylacetylene, isopropenylacetylene, and 2ethyl l-buten-B-yne; certain of the fulvene class of compounds such as fulvene itself, 6,6-dimethylfulvene, 6,6-diethylfulvene; acyclie nonconjugated dienes, such as 1,4-pentadiene, 1,5-hexadiene, 2-methyl-1,5hexadiene, 3,3-dimethyl-1,5-hexadiene, 1,7-octadieue, 1,9-decadiene, 6-

4 methyl-1,5-heptadiene, 1l-ethyl-l-,ll-triadecadiene; acetylenes, such as acetylene, vinylacetylene, isopropylacetylene; norbornene; and the like.

The relative amounts of the comonomers contained in the copolymer products of this invention can vary over a very wide range. In the case where ethylene and another l-monoolefin, such as propylene, are copolymerized, the copolymer usually comprises from 20 to 75 weight percent ethylene and from 20 to 75 weight percent proylene. When a termonorner is employed, it will generally make up from 0.5 to 20, preferably 1 to 10, weight percent of the polymer. The amount of the modifier employed in the polymerization is generally in the range of 5 to 500 millimoles per grams of propylene or other comonorner used with ethylene.

It is also frequently desirable to use a modifier in the polymerization. Such modifiers do not appear to enter into the polymer product but reduce the problem of agglomeration of polymer particles as they are produced. Such `agglomeration interferes With contact `between the monomers and the catalyst.

Compounds that are suitable for use as modifiers in the practice of the present invention include both conjugated and nonconjugated dienes. Examples of these compounds include 1,3-butadiene, isoprene, chloroprene, 3-vinyl-1-cyclohexene, 4-vinyl-1-cyclohexene, dipentene and 2,7-dimethyl-1,7-octadiene. The modifiers at the most are incorporated into the polymer structure only in trace amounts. As evidenced by a decrease in inherent viscosity of the products prepared in their presence, the modifiers function to control the molecular weight of the polymer product and provide a means for preparing stable polymer slurries of higher solids content than are otherwise obtainable. It is usually preferred to employ 1,3-butadiene in the preparation of the copolymers and terpolymers. The other modifiers are particularly useful in preparing copolymers although they can also be employed in the preparation of terpolymers. In addition to the other advantages mentioned, the modifiers, particularly 1,3-butadiene, function to control the propylene content of the ethylenepropylene copolymers and terpolymers, i.e., the propylene content can be maintained at a lower level than is normally obtained when the modifier is absent.

The present process is conducted at a temperature below about 60 F. The low temperature insures the formation of the polymer product as a slurry. It is usually not desirable to operate at a temperature below 310 F. in view of the slower reaction rates as the temperature is reduced. The polymerization is generally carried out at a pressure such that the larger proportion of the materials present are in the liquid phase but at the boiling point of the reaction mixture. Obviously, the pressure selected depends upon a number of factors including the composition of the mixture in the reaction zone and the temperature at which the polymerization is conducted. However, the range of 20 to 100 p.s.i.a. is generally used.

The particular catalyst used is one of the type which has become known as 'a coordination type catalyst. These generally include at least one reducing compound of a metal of Groups I, II, III, IV-A and V-A and at least one compound of a reducible polyvalent transition metal of Groups IV-B, V-B, VI-B, VII-B, and VIII, according to the chart shown on pages 448-449 of the 43rd edition of Handbook of Chemistry and Physics, copyright 1961, The Chemical Rubber Publishing Co. Such catalysts have been extensively explored by others in this field and the term coordination catalyst identifies such catalysts to those skilled in the art. For additional information and specific examples, reference is made to Linear and Stereoregular Addition Polymers by Gaylord and Mark, copyright 1959 by Interscience Publishers, Inc. Chapter VII is particularly pertinent.

Also present during the polymerization is a low molecular Weight non-reactive hydrocarbon. Reference has been made to ethane as an example of this material.

6 other suitable compounds include the lower molecular (d) introducing, into said wash zone, a wash liquid weight aliphatic hydrocarbons such as propane, the comprising the hydrocarbon of step I(b) not introbutanes, the pentanes, the hexanes, and aromatic comduced into said reaction zone and countercurrently pounds such as benzene and toluene. The selection of the washing said slurry with said wash liquid therein particular non-reactive hydrocarbon will depend upon the r to separate at least a portion of the catalyst and unconditions desired in the reaction zone. 'In general, the a reacted olens from said slurry; lower molecular weight materials in the `group are re- (e) passing the resulting wash zone eluent containferred as ithe polymerization temperature is reduced. ing catalyst and unreacted oleins from said wash The polymerization process of this invention is conzone to said reaction zone;I ducted in the absence of material-s which may have a lo (f) separating any remaining unreacted olefin, low modeleterious effect on the catalyst. These ma-terials nlecular weight hydrocarbon, and a further portion clude oxygen, carbondioxide, and water. It is usually of the catalyst from the washed polymer slurry; desirable that the monomers be substantially free from (g) recovering apolymer slurry; these materials as well as from -other materials which (h) removing an overhead vapor stream from the upmay tend to inactivate the catalyst before contacting the -per portion of said reaction zone and cooling said monomers with the catalyst. overhead stream to condense same;

It is also desirable that air and moisture be removed (i) passing the condensed overhead stream to an acfrom the reaction vessel before the reaction is carried cumulation zone; out. (j) controlling feed of said low molecular weight, non- The following example illustrates a specific embodireactive hydrocarbon in response to changes of ment of the process but it should not be considered liquid level in said accumulation zone to maintain unduly limiting. a constant amount thereof in fthe system so as to EXAMPLE maintain a desired boiling point in said reaction zone; This example hJSTe'eS the Operation 0f the System 0f 25 (k) recycling liquid from said accumulation zone to my invention as it is shown in the drawing. Suitable op- `,Said reaction zone; and eration is obtained when the reaction zone is maintained |(1) `wrm-011mg 110W of Said recycled Stream so as to at 85 F and 40 PSa While the Steam Stripping Zone maintain a constant liquid level in said reaction is operated at 90 'F and l`5 p.s.i.a. The catalyst is a mix- Z0ne ture of ethylaluminum sesquichloride and vanadium tet- 2 The process according to Claim 1 wherein the monorachloride. -Dicyclopentadiene is used as the termonomer mer introduced in Step (a) is ethylene, and butadiene S Sed 3S a medie The ehane and 3. The process according to claim 2 wherein the hydroethylene are supplied directly to the polymerization zone carbon introduced in Step (rb) is propylene and the hydroand all of the make-up propylene is supplied to the lower carbon introduced in Step (d) is ethane, end portion of lthe wash column. 4. The process according to claim 2 wherein the hydro- A material balance, where the amounts are given in carbon introduced in step (b) is ethane and the hydrocarpounds per stream day is shown in the following table: bon introduced in step (d) is propylene.

Makeup Makeup Reactor Reactor Wash Hydro- Makeup Makeup Dicyelo Buta- Make-up Make-up Make-up Vapor Slurry Column Stripper Stripper carbon Propyl- Ethyl- Pentadiene Ethan@ V014 EASC Ellu- Elu- Over- Feed Bottoms Recycle ene ene diene ent ent head Stream Pmpyiene 53, 900 44,000 127,000 108,800 07,000 e7, 900 Ethylene 80,500 44,000 8,400 49, 200 1,000 1, 000 Dicyclopenta- As many possible embodiments can be made of this 5. In a process wherein ethylene, propylene, and a noninvention without departing from the scope thereof, it is conjugated diolen are polymerized with a catalyst which to be understood that all matter herein set forth is to forms on mixing (1) at least one reducing compound of .be interpreted as illustrative and not as unduly limiting the metals of Groups I, II, III, lV-A and V-A and (2) the invention. at least one compound of a reducible polyv-alent transition That which is claimed is: metal of Groups lV-B, V-B, Vl-B, VII-B, and VIII in a 1. In a process comprising polymerizing a mixture of reaction zone in the presence of a low molecular, nonat least two l-monoolefns in a reaction zone with a reactive hydrocarbon used to maintain the polymerization polymerization catalyst in the presence of a low molecutemperature at -310 to -60- F. and the polymerization lar weight, nonreactive hydrocarbon which acts to mainpressure at 20 to 100 p.s.i.a. so as to form a liquid tain the reaction mixture at a desired boiling point, said lslurry of a terpolymer of the olens, the improvement polymerization being performed under conditions such comprising the steps: that a slurry of solid polymer is formed in `said reaction (a) introducing the catalyst, non-conjugated diolen zone, the improvement comprising the steps: and ethylene into said reaction zone;

I(a) A introducing monomer comprising at least y011e of (b) introducing one of (l) propylene and (2) low said l-monooleins and the catalyst into said reacmolecular weight, nonreactive hydrocarbon directly tion zones; into said reaction zone;

(b) introducing one of (l) said low molecular weight, (c) passing said slurry from said reaction zone to a non-reactive hydrocarbon and (Q) one of said wash zone; l-monoolen other than that introduced into step (d) introducing, into said wash zone, a 'wash liquid (a) into said reaction zone; comprising the hydrocarbon of step (b) not intro- |(c) passing said slurry from said reaction zone to a duced into said reaction zone and countercurrently wash zone; washing said slurry with said wash liquid thereinto separate at least a portion of the catalyst and unreacted olens from said slurry;

(e) passing the resulting wash zone efuent containing catalyst and unreacted oletns from said wash zone to said reaction zone;

(f) separating any remaining unreacted olen, low

molecular weight hydrocarbon, and a further portion of the catalyst from the washed terpolymer slurry;

(g) recovering a terpolymer slurry;

(h) removing an overhead vapor stream containing propylene, ethylene, and low molecular weight, nonreactive hydrocarbon from the upper portion of said reaction zone;

(i) compressing and cooling said overhead stream to condense same;

(j) passing the condensed overhead stream to an accumulation zone;

(k) controlling feed of low molecular weight, nonreactive hydrocarbon in response to changes of liquid level in lsaid accumulation zone to maintain a constant amount thereof in the system so as to maintain a desired boiling point in said reaction zone;

(l) recycling liquid from said accumulation zone to said reaction zone; and

(m) controlling flow of said recycled stream to maintain a constant liquid level in said reaction zone.

6. The process of claim 5 wherein said nonconugated diolen is dicyclopentadiene, said catalyst is an ethylaluminum sesquichloridevanadium tetrachloride catalyst, and said low molecular Weight, nonreactive hydrocarbon is ethane.

7. The process of claim 6 wherein makeup ethane and ethylene are fed directly to the reaction zone and makeup propylene is fed to said wash zone.

8. The process of claim 6 wherein makeup ethylene and propylene are fed directly to the reaction zone and makeup ethane is fed to said wash zone.

References Cited UNITED STATES PATENTS 2,484,384 10/ 1949 Levine et al 260-92.8 3,108,094 10/ 1963 Morgan 26094.9 3,197,454 7/ 1965 Plaster 260-94.9 3,254,071 5/ 1966 Morgan et al. 260-94.9 3,280,090 10/1966 Scoggin 260-94.9 3,291,780 12/1966 Gladding et al 260-80.5

JOSEPH L. SCHOFER, Primary Examiner.

HARRY WONG, IR., Assistant Examiner.

U.S. Cl. X.R 

